ACS Catalysis
Research Article
Scheme 5. Large-Scale Production of 6m
Scheme 6. Metal-Catalyzed Cross Coupling Reaction of Diphenyl Phosphinic Acid with Iodobenzene and Phenylboronic Acid15
ascribed to the fact that electron-poor aryl groups are
transferred more readily than electron-rich aryl groups in the
arylation reaction of unsymmetric diaryliodonium salts with
P(O)−OH compounds.12b
AUTHOR INFORMATION
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Corresponding Author
Notes
In order to demonstrate the practical application of this
method, we performed a large-scale reaction of di-(4-
bromophenyl) iodonium triflate 5c (20 mmol) with 1a (24
mmol) and obtained 6g in 83% yield. The byproduct 1-bromo-
4-iodobenzene was recovered in 81% yield (Scheme 5).
With traditional metal-catalyzed cross-coupling reaction in
mind, we used copper salts (e.g., CuI, CuBr, CuO, Cu(OAc)2)
as well as palladium salts (e.g., Pd(OAc)2, PdCl2) to promote
the reaction of diphenyl phosphinic acid with iodobenzene or
phenylboronic acid under the present reaction conditions but
found no generation of coupling products. It is plausibly that
there is easy coordination of diphenyl phosphinic acid with the
metals to form phosphoryl-metal intermediates rather than the
activation of iodobenzene or phenylboronic acid. It is deduced
that in comparison with the other nucleophiles, the
corresponding cross coupling reaction is much more difficult
to undergo due to the strong acidity of the P(O)−OH
compounds (Scheme 6).15
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank the NSFC (U1162109, 21273066, 21273067),
Program for Changjiang Scholars and Innovative Research
Team in University (IRT1238), and the Fundamental Research
Funds for the Central Universities (Hunan University) for
financial support. C.-T.A. thanks HNU (Hunan University) for
an adjunct professorship.
REFERENCES
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ASSOCIATED CONTENT
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* Supporting Information
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Information of experimental procedures and methods,
characterization data, and NMR spectra of organic
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ACS Catal. 2015, 5, 537−543